TW201930455A - Epoxy resin composition for sealing ball grid array package, epoxy resin cured product and electronic component device - Google Patents

Abstract

The epoxy resin composition for sealing a BGA package contains an epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g/eq or less, and an inorganic filler containing alumina particles and ceria particles, the inorganic filler The content ratio is from 65% by volume to 85% by volume, and the ratio of the cerium oxide particles to the total amount of the alumina particles and the cerium oxide particles is from 10% by mass to 15% by mass.

Description

Epoxy resin composition, epoxy resin cured product and electronic component device for ball grid array package sealing

The present disclosure relates to an epoxy resin composition, an epoxy resin cured product, and an electronic component device for sealing a ball grid array package.

The demand for high-density mounting due to miniaturization and thinning of electronic equipment has rapidly increased in recent years. Therefore, with respect to the semiconductor package, a surface mount type suitable for high-density mounting in place of the previous stitch insertion type has become mainstream. The surface mount type semiconductor package is mounted by directly soldering to a printed circuit board or the like. As a general mounting method, a method of heating and mounting the entire semiconductor package by an infrared reflow method, a vapor phase reflow method, a solder dipping method, or the like can be exemplified.

In recent years, in order to further increase the mounting density, a surface mount package such as a ball grid array (hereinafter also referred to as BGA) has been widely used in a surface mount type semiconductor package. The BGA package is a single-sided resin-sealed package in which a semiconductor element mounting surface of a substrate is sealed with a resin composition. As the resin composition for sealing, an epoxy resin composition can be widely used from the viewpoint of balance of various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to an insert.

On the other hand, in recent years, in the field of electronic components, the speed and density have been increasing, and the amount of heat generated by electronic components has increased significantly. In addition, the demand for electronic components operating at high temperatures has increased. Therefore, an improvement in thermal conductivity is required for a cured product of a plastic, particularly an epoxy resin, used in an electronic component. In particular, in the BGA package, the high thermal conductivity of the resin composition for sealing is required in accordance with the requirements for miniaturization and high density. As a method of improving the thermal conductivity of the cured product of the epoxy resin, there is reported a method in which an inorganic filler having high thermal conductivity such as alumina is used, and the inorganic filler is added by a resin having a low viscosity and a small amount of fine particle cerium oxide. The filling amount (for example, refer to Patent Document 1).
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent No. 4188634

[Problems to be solved by the invention]

However, if the amount of alumina filled in the epoxy resin composition is increased for the purpose of high thermal conductivity, the fluidity may be lowered to impair the formability. In Patent Document 1, a small amount of fine particle cerium oxide is mixed into an alumina filler, and a high-filling of the filler is achieved using a specific biphenyl-type epoxy resin having a low viscosity. However, in this method, there is room for improvement in fluidity. Further, with the reduction in thickness of the BGA package, the narrow pitch of the bonding wires, the increase in the number of stitches, and the increase in density, higher fluidity is also required.

Therefore, an object of the present invention is to provide an epoxy resin composition for sealing a BGA package having excellent fluidity and excellent thermal conductivity during curing, and an epoxy resin cured product obtained by curing the epoxy resin composition. And an electronic component device including an element sealed by the epoxy resin cured product.
[Means for solving the problem]

The means for solving the above problems include the following embodiments.
<1> An epoxy resin composition for sealing a ball grid array package, comprising an epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g/eq or less, and an inorganic filler containing alumina particles and cerium oxide particles material,
The content of the inorganic filler is from 65% by volume to 85% by volume.
The ratio of the cerium oxide particles to the total amount of the alumina particles and the cerium oxide particles is 10% by mass to 15% by mass.
<2> The epoxy resin composition for sealing a ball grid array package according to <1>, further comprising a curing accelerator, wherein the curing accelerator contains an organic phosphorus compound.
<3> The epoxy resin composition for sealing a ball grid array package according to <1>, wherein the phenolic hardener comprises a phenol resin having three or more phenolic hydroxyl groups in one molecule.
The epoxy resin composition for sealing a ball grid array package according to any one of <1> to <3> wherein the phenol hardener comprises a triphenylmethane type phenol resin.
<5> A cured epoxy resin composition obtained by curing the epoxy resin composition for sealing the ball grid array package according to any one of <1> to <4>.
<6> An electronic component device having an element, a cured epoxy resin as described in <5>, and having a ball grid array package.
[Effects of the Invention]

According to the present disclosure, it is possible to provide an epoxy resin composition for sealing a BGA package which is excellent in fluidity and excellent in thermal conductivity during curing, an epoxy resin cured product obtained by curing the epoxy resin composition, and including An electronic component device of an element sealed by the epoxy resin cured product.

Hereinafter, embodiments for carrying out the invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including the element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the invention.

In the present disclosure, the term "step" includes the steps other than the steps independent of the other steps, even if it is not clearly distinguishable from other steps, as long as the purpose of the step is achieved.
In the present disclosure, the numerical values described before and after the "~" in the numerical range indicated by "~" are used as the minimum value and the maximum value, respectively.
In the numerical range recited in the present disclosure, the upper limit or the lower limit described in one numerical range may be replaced with the upper or lower limit of the numerical range described in other stages. In addition, in the numerical range described in the present disclosure, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, each component may also contain a plurality of conforming substances. When a plurality of substances corresponding to the respective components are present in the composition, the content or content of each component means the total content or content of the plurality of substances present in the composition unless otherwise specified.
In the present disclosure, a plurality of particles corresponding to the respective components may also be included. In the case where a plurality of particles conforming to the respective components are present in the composition, the particle diameter of each component means the value of the mixture of the plurality of particles present in the composition unless otherwise specified.

<Epoxy Resin Composition for BGA Package Sealing>
The epoxy resin composition for sealing a BGA package of the present invention (hereinafter also referred to as an epoxy resin composition) contains an epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g/eq or less, and alumina particles. An inorganic filler of cerium oxide particles, wherein the content of the inorganic filler is from 65 to 85% by volume, and the cerium oxide particles are combined with respect to the total amount of the alumina particles and the cerium oxide particles The ratio is from 10% by mass to 15% by mass.

In general, when the content of the alumina particles is increased in order to increase the thermal conductivity of the cured product, the fluidity is lowered. On the other hand, the epoxy resin composition of the present invention has excellent thermal conductivity at the time of hardening and maintains good fluidity. Although the reason is not clear, it can be considered as follows. In the epoxy resin composition, the content of the inorganic filler is set to be 65% by volume to 85% by volume, and the ratio of the cerium oxide particles to the total amount of the alumina particles and the cerium oxide particles is When the cerium oxide particles are contained in an amount of 10% by mass to 15% by mass, the thermal conductivity can be ensured by the alumina. On the other hand, the resin component and the cerium oxide particles are appropriately present around the alumina particles to reduce the alumina. Since the particles are rubbed between the particles, the decrease in fluidity can be suppressed. In addition, it is considered that when the inorganic filler is set to such a setting and a phenol curing agent having a hydroxyl equivalent of 120 g/eq or less is used as a curing agent, the crosslinking density after curing can be ensured without impairing fluidity. Improves thermal conductivity.

The epoxy resin compositions of the present disclosure can be used for the sealing of BGA packages. The BGA package refers to a semiconductor package in which a plurality of metal bumps are arranged in a lattice on a substrate of a package. The BGA package is fabricated by mounting an element on a surface of a substrate on which metal bumps are formed on the back surface, and bonding the element to a wiring formed on the substrate by bumping or wire bonding, and then sealing the element. A chip size package (CSP) or the like that reduces the outer diameter size to the same size as the element is also one form of the BGA package.

[Epoxy resin]
The epoxy resin composition of the present disclosure contains an epoxy resin. The epoxy resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule. The epoxy resin is not particularly limited, and examples thereof include a phenol compound selected from the group consisting of phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, and α-naphthol, β. - at least one phenolic compound in a group consisting of a naphthol compound such as naphthol or dihydroxynaphthalene, and a phenolic aldehyde obtained by condensation or co-condensation with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde or propionaldehyde under an acidic catalyst A phenol varnish type epoxy resin (phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, etc.) which is epoxidized by a varnish resin; the phenolic compound, benzaldehyde, salicylaldehyde, etc. a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by condensation or co-condensation of an aromatic aldehyde compound under an acidic catalyst; the phenol compound and a naphthol compound and an aldehyde are obtained a copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained by co-condensation of a compound under an acidic catalyst; a diphenylmethane type epoxy resin as a diglycidyl ether of bisphenol A or bisphenol F; Alkylo substituted or unsubstituted biphenol a biphenyl type epoxy resin of diglycidyl ether; a stilbene type epoxy resin as a diglycidyl ether of a stilbene phenol compound; a sulfur atom-containing ring as a diglycidyl ether of bisphenol S or the like Oxygen resin; epoxy resin as a glycidyl ether of an alcohol such as butanediol, polyethylene glycol or polypropylene glycol; and a polycarboxylic acid compound such as phthalic acid, isophthalic acid or tetrahydrophthalic acid. a glycidyl ester type epoxy resin of glycidyl ester; a glycidol which is obtained by substituting an active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane or iso-cyanuric acid with a glycidyl group An amine type epoxy resin; a dicyclopentadiene type epoxy resin which is obtained by epoxidizing a cocondensation resin of a dicyclopentadiene and a phenol compound; and a epoxidized olefin bond in the molecule Epoxidized vinyl cyclohexene, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-5, An alicyclic epoxy resin such as 5-spirocyclo(3,4-epoxy)cyclohexane-m-dioxane; as a p-xylene-modified phenol resin a p-xylene modified epoxy resin of glyceryl ether; a meta-xylene modified epoxy resin as a glycidyl ether of a meta-xylene-modified phenol resin; a terpene modification of a glycidyl ether as a terpene-modified phenol resin Epoxy resin; dicyclopentadiene modified epoxy resin as glycidyl ether of dicyclopentadiene modified phenol resin; cyclopentadiene modified as glycidyl ether of cyclopentadiene modified phenol resin Epoxy resin; polycyclic aromatic ring modified epoxy resin as glycidyl ether of polycyclic aromatic ring modified phenol resin; naphthalene type epoxy resin as glycidyl ether of naphthalene ring-containing phenol resin; halogenated phenol novolac Type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing an olefin bond by a peroxy acid such as peracetic acid; An aralkyl type epoxy resin obtained by epoxidizing an aralkyl type phenol resin such as a base resin or a naphthol aralkyl resin. Further, an epoxy resin such as an epoxide of an anthrone resin or an epoxide of an acrylic resin may be mentioned. The epoxy resins may be used alone or in combination of two or more.

In the epoxy resin, from the viewpoint of balance between reflow resistance and fluidity, it is preferably selected from the group consisting of a biphenyl type epoxy resin, a stilbene type epoxy resin, and a diphenylmethane type epoxy resin. Resin, sulfur atom-containing epoxy resin, novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin, copolymer type epoxy resin, and aralkyl type epoxy resin Any one of the group consisting of at least one epoxy resin (referred to as "specific epoxy resin"). The specific epoxy resins may be used alone or in combination of two or more.

When the epoxy resin contains a specific epoxy resin, the content of the specific epoxy resin is preferably 30% by mass or more, and more preferably 50%, based on the performance of the specific epoxy resin. More than % by mass.

In the specific epoxy resin, from the viewpoint of fluidity, it is preferably selected from the group consisting of a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, and a sulfur atom-containing ring. At least one of the group consisting of oxygen resins is preferably selected from the group consisting of a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, and an aralkyl group from the viewpoint of heat resistance. At least one of the group consisting of epoxy resins. Among them, from the viewpoint of fluidity, a biphenyl type epoxy resin is also preferable.

The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following formula (II) is preferred. In the epoxy resin represented by the following general formula (II), it is also possible to obtain, as a commercially available product, 3, 3', 5 when the position at which the oxygen atom in R ⁸ is substituted is 4 and 4'. 5 'is methyl and R ⁸ is other than a hydrogen atom YX-4000H (manufactured by Mitsubishi chemical Co., Ltd., trade name), all of R ⁸ is 4,4-bis (2,3-hydrogen atoms, When oxypropoxy)biphenyl is used, all R ⁸ are hydrogen atoms, and the position where the oxygen atom in R ⁸ is substituted is 3, 3', and 5, 5' is methyl at the 4 and 4' positions. In addition, R ⁸ is a mixture of YL-6121H (Mitsubishi Chemical Co., Ltd., trade name) in the case where R ⁸ is a hydrogen atom.

[Chemical 1]

In the formula (II), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, and may be all the same or different. n is an average value and represents a number from 0 to 10.

In the formula (II), R ^{8 is} preferably independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and further preferably a hydrogen atom or a methyl group. .

In the formula (II), n represents a number of 0 to 10, preferably 0 to 4. When n is 10 or less, the melt viscosity of the resin component does not become excessively high, and the viscosity at the time of melt molding of the epoxy resin composition is lowered, and the filling failure and the bonding wire (connecting the component to the lead wire) can be suppressed. The generation of deformation or the like of the gold wire).

As a more specific preferred biphenyl type epoxy resin, 4,4'-bis(2,3-epoxypropoxy)-3 is exemplified in terms of fluidity and reflow resistance. 3',5,5'-tetramethylbiphenyl, in terms of fluidity, formability, and heat resistance, 4,4'-bis(2,3-epoxypropoxy)-linked benzene.

The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following formula (IV) is preferred. In the epoxy resin represented by the following general formula (IV), it is also possible to obtain, as a commercially available product, a case where all of R ¹¹ are a hydrogen atom, and a position at which an oxygen atom in R ¹² is substituted is 4 and 4'. YSLV-80XY (Nippon Steel & Metal Co., Ltd., trade name) in which the 3,3', 5, and 5' positions are a methyl group and R ¹² is a hydrogen atom.

[Chemical 2]

In the formula (IV), R ¹¹ and R ^{12 each} independently represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. n is an average value and represents a number from 0 to 10.

In the formula (IV), R ¹¹ and R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a hydrogen atom or a methyl group. .
In the formula (IV), n is preferably from 0 to 4.

The triphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a compound having a triphenylmethane skeleton as a raw material. For example, an epoxy resin obtained by glycidyl etherification of a triphenylmethane type phenol resin such as a novolac type phenol resin having a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is more preferably used. The epoxy resin represented by the formula (VIII). In the epoxy resin represented by the following formula (VIII), 1032H60 (Mitsubishi Chemical Co., Ltd., trade name) and EPPN-502H (Japanese) in which i is 0 and k is 0 can be obtained as a commercial product. Pharmaceutical Co., Ltd., trade name) and so on.

[Chemical 3]

In the formula (VIII), R ¹⁷ and R ^{18 each} represent a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. i each independently represents an integer of 0 to 3, and k each independently represents an integer of 0 to 4. n is an average value and represents a number from 0 to 10. Further, in the formula (VIII), a hydrogen atom existing on the aromatic ring is not displayed.

In the formula (VIII), R ¹⁷ and R ¹⁸ are each independently an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
In the formula (VIII), n is preferably from 0 to 4.

In one embodiment, the epoxy resin composition preferably contains a biphenyl type epoxy resin, a diphenylmethane type epoxy resin, and a triphenyl group from the viewpoint of reflow resistance and fluidity. At least one of the group consisting of methane type epoxy resins. The epoxy resin composition may contain at least two selected from the group consisting of the epoxy resins, and may contain any of the epoxy resins.

In an embodiment in which the epoxy resin composition contains a biphenyl type epoxy resin, the content of the biphenyl type epoxy resin is preferably 60% by mass to 100% by mass based on the total amount of the epoxy resin, and is preferably 70% by mass to 100% by mass, and more preferably 80% by mass to 100% by mass.
In another embodiment in which the epoxy resin composition contains a biphenyl type epoxy resin, the content of the biphenyl type epoxy resin is preferably from 5% by mass to 60% by mass based on the total amount of the epoxy resin, more preferably It is 10% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass.
In an embodiment in which the epoxy resin composition contains a diphenylmethane type epoxy resin, the content of the diphenylmethane type epoxy resin is preferably from 5% by mass to 45% by mass based on the total amount of the epoxy resin. More preferably, it is 5% by mass to 35% by mass, and further preferably 5% by mass to 25% by mass.
In an embodiment in which the epoxy resin composition contains a triphenylmethane type epoxy resin, the content of the triphenylmethane type epoxy resin is preferably from 25% by mass to 85% by mass based on the total amount of the epoxy resin. More preferably, it is 35 mass% - 75 mass%, and further preferably 45 mass% - 65 mass%.

The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin is preferably from 100 g/eq to 1000 g/eq, more preferably from 150 g/eq to 500, from the viewpoint of balance of various properties such as moldability, reflow resistance, and electrical reliability. g/eq. The epoxy equivalent of the epoxy resin is set to a value measured by a method according to Japanese Industrial Standards (JIS) K 7236:2009.

In the case where the epoxy resin is a solid, the softening point or melting point thereof is not particularly limited. The softening point or melting point of the epoxy resin is preferably from 40 ° C to 180 ° C from the viewpoint of moldability and reflow resistance, and is more preferably from the viewpoint of workability in preparation of the epoxy resin composition. 50 ° C ~ 130 ° C. The melting point of the epoxy resin is a value measured by Differential Scanning Calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method according to JIS K 7234:1986 (ring and ball method). .

The content of the epoxy resin in the epoxy resin composition is preferably from 0.5% by mass to 50% by mass, and more preferably from 2% by mass to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability and the like. .

The epoxy resin may also contain an epoxy resin (also referred to as a polyfunctional epoxy resin) having three or more epoxy groups in one molecule. As described later, when the epoxy resin composition contains an organic phosphorus compound as a curing accelerator, the polyfunctionality relative to the total mass of the epoxy resin is controlled from the viewpoint of controlling the warpage behavior of the package after reflow. The content of the epoxy resin is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and particularly preferably substantially 0% by mass. The content ratio of "substantially 0% by mass" means a content ratio in which the effect of the polyfunctional epoxy resin on controlling the warpage behavior of the package after reflow is not observed.

[Specific Phenol Hardener]
The epoxy resin composition of the present invention contains a phenol curing agent having a hydroxyl group equivalent of 120 g/eq or less (hereinafter also referred to as a specific phenol curing agent). The specific phenol curing agent is not particularly limited as long as it has a phenolic hydroxyl group and a hydroxyl equivalent of 120 g/eq or less. The specific phenol curing agent may be a low molecular phenol compound or a phenol resin obtained by polymerizing a low molecular phenol compound. From the viewpoint of thermal conductivity, the specific phenol curing agent is preferably a phenol resin. The specific phenol curing agent may be used alone or in combination of two or more.

The specific phenol curing agent preferably contains a phenol resin having two or more phenolic hydroxyl groups in one molecule, more preferably a phenol resin having three or more phenolic hydroxyl groups in one molecule (also referred to as a polyfunctional phenol resin). .

The phenol resin is not particularly limited, and examples thereof include a copolymerization resin of a biphenyl type phenol resin, an aralkyl type phenol resin, a dicyclopentadiene type phenol resin, a benzaldehyde type phenol resin, and an aralkyl type phenol resin. , triphenylmethane type phenol resin, and the like. Among them, a triphenylmethane type phenol resin is preferred.

The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained by using a compound having a triphenylmethane skeleton as a raw material. For example, a phenol resin represented by the following formula (XVI) is preferred.

In the phenol resin represented by the following formula (XVI), MEH-7500 (Mingwa Chemical Co., Ltd., trade name) in which i is 0 and k is 0 can be obtained as a commercial product.

[Chemical 4]

In the formula (XVI), R ³⁰ and R ^{31 each} represent a monovalent organic group having 1 to 18 carbon atoms, and may be all the same or different. i is independently an integer of 0 to 3, and k is independently an integer of 0 to 4, respectively. n is an average value and is a number from 0 to 10. Further, in the formula (XVI), a hydrogen atom existing on the aromatic ring is not displayed.

In the formula (XVI), R ³⁰ and R ³¹ are each independently an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
In the formula (XVI), n is preferably from 0 to 5.

The specific phenolic hardener has a hydroxyl equivalent of 120 g/eq or less, preferably 110 g/eq or less, more preferably 100 g/eq or less. When the hydroxyl group equivalent of the phenol curing agent is 120 g/eq or less, good moldability tends to be obtained. In addition, the lower limit of the hydroxyl group equivalent is not particularly limited, and is preferably 50 g/eq or more, more preferably 60 g/eq or more, from the viewpoint of balance of various characteristics such as reflow resistance and electrical reliability. 70 g/eq or more. The preferred hydroxyl equivalent weight is preferably in the range of 50 g/eq to 120 g/eq, more preferably 60 g/eq to 115 g/eq, and still more preferably 70 g/eq to 110 g/eq.

The hydroxyl equivalent of the specific phenol curing agent is set to a value measured by a method in accordance with JIS K 0070:1992.

In the case where the specific phenol curing agent is a solid, the melting point or softening point thereof is not particularly limited. The melting point or softening point of the specific phenol curing agent is preferably from 50 ° C to 250 ° C, more preferably from 65 ° C to 200 ° C, still more preferably from 70 ° C to 170 ° C.

The melting point or softening point of the specific phenol curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.

The content ratio of the epoxy resin to the specific phenol curing agent in the epoxy resin composition is preferably a ratio of the number of equivalents of the hydroxyl group of the specific phenol curing agent to the number of equivalents of the epoxy group of the epoxy resin (the equivalent of the hydroxyl group) The number of the number of the epoxy groups is set to be in the range of 0.5 to 2.0, more preferably set to be 0.7 to 1.5, and more preferably set to be 0.8 to 1.3. When the ratio is 0.5 or more, the curing of the epoxy resin is sufficient, and the heat resistance, moisture resistance, and electrical properties of the cured product tend to be excellent. In addition, when the ratio is 2.0 or less, the amount of the phenolic hydroxyl group remaining in the cured resin is suppressed, and the electrical properties and the moisture resistance tend to be excellent.

The epoxy resin composition may further contain a hardener other than the specific phenolic hardener as a hardener. Examples of the curing agent other than the specific phenol curing agent include phenol resins other than the specific phenol curing agent generally used in the field. The curing agent other than the specific phenol curing agent may be used alone or in combination of two or more.

When the epoxy resin composition contains a curing agent other than the specific phenol curing agent, the content of the specific phenol curing agent in the total amount of the curing agent is preferably 60 from the viewpoint of sufficiently exhibiting the performance of the specific phenol curing agent. The mass% or more is more preferably 75% by mass or more, and further preferably 90% by mass or more.

In the case where the epoxy resin composition contains a hardener other than the specific phenol hardener, the content ratio of the epoxy resin to the total hardener is preferably an epoxy equivalent to the epoxy resin according to the number of equivalents of the functional group of the total hardener. The ratio of the number of equivalents of the group (the number of equivalents of the functional group of the curing agent / the number of equivalents of the epoxy group) is set. For example, it is preferable to set the ratio so as to be in the range of 0.5 to 2.0, more preferably set it so as to be 0.7 to 1.5, and it is preferable to set it so as to be 0.8 to 1.3. .

[Inorganic filler]
The epoxy resin composition of the present invention contains an inorganic filler comprising alumina particles and cerium oxide particles. The content of the inorganic filler is from 65% by volume to 85% by volume based on the total volume of the composition, and the ratio of the cerium oxide particles to the total amount of the alumina particles and the cerium oxide particles is from 10% by mass to 15% by mass. %. The inorganic filler may also contain an inorganic filler other than the alumina particles and the ceria particles, and the inorganic filler preferably contains alumina particles and cerium oxide particles. Examples of the cerium oxide particles include spherical cerium oxide, crystalline cerium oxide, and the like.

The volume average particle diameter of the inorganic filler is not particularly limited. The volume average particle diameter of the inorganic filler is, for example, preferably from 0.1 μm to 80 μm, more preferably from 0.3 μm to 50 μm. When the volume average particle diameter of the inorganic filler is 0.1 μm or more, the viscosity of the epoxy resin composition tends to be suppressed from increasing. When the volume average particle diameter of the inorganic filler is 80 μm or less, the miscibility of the epoxy resin composition and the inorganic filler is improved, and the state of the package obtained by curing is further homogenized to suppress unevenness in characteristics. There is a tendency that the filling property in a narrow region tends to be improved. Further, the particle size distribution of the inorganic filler preferably has a maximum value in the range of 0.1 μm to 80 μm.

The volume average particle diameter of the alumina particles is, for example, preferably from 0.1 μm to 80 μm, more preferably from 0.3 μm to 50 μm. When the volume average particle diameter of the alumina particles is 0.1 μm or more, the viscosity of the epoxy resin composition tends to be suppressed from increasing. When the volume average particle diameter of the alumina particles is 80 μm or less, the miscibility of the epoxy resin composition and the alumina particles is improved, and the state of the package obtained by curing is further homogenized to suppress unevenness in characteristics. There is a tendency that the filling property in a narrow region tends to be improved.

Further, the volume average particle diameter of the cerium oxide particles is, for example, preferably from 0.1 μm to 50 μm, more preferably from 0.3 μm to 30 μm, still more preferably from 0.5 μm to 20 μm. When the volume average particle diameter of the cerium oxide particles is 50 μm or less, the fluidity tends to be improved.

In the present disclosure, the volume average particle diameter of the inorganic filler may be a wet particle size distribution measuring device using a dry particle size distribution meter or a slurry obtained by dispersing an inorganic filler in water or an organic solvent. Determination. In particular, in the case of containing particles of 1 μm or less, it is preferably measured using a wet particle size distribution meter. Specifically, the water slurry in which the concentration of the inorganic filler is adjusted to about 0.01% by mass can be treated by a bath ultrasonic cleaning machine for 5 minutes, and a laser diffraction type particle size measuring device (LA-960, Horiba, Ltd.) can be used. Co., Ltd.) performs a test to determine the volume average particle diameter of the inorganic filler based on the average value of the total particles detected. In the present disclosure, the volume average particle diameter is a particle diameter (D50) when the accumulation on the small-diameter side is 50% in the volume-based particle size distribution.

From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical, and the particle size distribution of the inorganic filler is preferably distributed over a wide range. For example, it is preferable that 70% by mass or more of the inorganic filler is spherical particles, and the particle diameter of the spherical particles is distributed over a wide range of 0.1 μm to 80 μm. Since such an inorganic filler is easily formed into a densely packed structure by mixing particles having different sizes, the viscosity of the epoxy resin composition can be suppressed and the fluidity can be obtained even if the content of the inorganic filler is increased. The tendency of an excellent epoxy resin composition.

The inorganic filler may be, for example, an alumina particle having a volume average particle diameter of 1 μm or less, and a volume average particle, from the viewpoint of further improving the fluidity of the epoxy resin composition and the thermal conductivity when the cured product is formed. Those having a diameter of 1 μm or less of cerium oxide particles.
The inorganic filler is an alumina particle containing a volume average particle diameter of 1 μm or less, and a particle size distribution (frequency) by which the volume of the inorganic filler is determined by, for example, a ceria particle having a volume average particle diameter of 1 μm or less. Distribution) to confirm.

In addition, the inorganic filler may have a volume average particle diameter of 1 μm or less from the viewpoint of improving the fluidity of the epoxy resin composition and the thermal conductivity at the time of forming the cured product and reducing the warpage of the package. The alumina particles and the cerium oxide particles having a volume average particle diameter of more than 1 μm and 20 μm or less, preferably 5 μm to 15 μm. The inorganic filler is an alumina particle having a volume average particle diameter of 1 μm or less, and a cerium oxide particle having a volume average particle diameter of more than 1 μm and 20 μm or less, preferably 5 μm to 15 μm, for example, The volume distribution (frequency distribution) based on the volume of the inorganic filler was determined.

The content of the inorganic filler is from 65% by volume to 85% by volume based on the total volume of the composition, and is preferably from 68% by volume to 80% by volume, more preferably from the viewpoint of balance of characteristics such as thermal conductivity and fluidity. It is 70% by volume to 78% by volume.
Further, from the viewpoint of balance of characteristics such as thermal conductivity and fluidity, the content of the inorganic filler is preferably from 84% by mass to 95% by mass, more preferably from 85% by mass to 94% by mass based on the total mass of the composition. %, and further preferably 86% by mass to 92% by mass.

The ratio of the cerium oxide particles in the total amount of the alumina particles and the cerium oxide particles in the epoxy resin composition is from 10% by mass to 15% by mass, and from the viewpoint of balance of characteristics such as thermal conductivity and fluidity, It is preferably from 12% by mass to 14% by mass, and more preferably from 12% by mass to 13% by mass.

The inorganic filler other than the alumina particles and the ceria particles is not particularly limited, and examples thereof include glass, calcium carbonate, zirconium silicate, magnesium oxide, calcium niobate, tantalum nitride, aluminum nitride, and boron nitride. , tantalum carbide, industrial diamond, yttria, zirconia, zircon, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, mica, etc. Particles of inorganic substances, beads formed by spheroidizing these particles, and the like. Further, an inorganic filler having a flame retarding effect can also be used. Examples of the inorganic filler having a flame retarding effect include particles of a composite metal hydroxide such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, and zinc borate. The inorganic filler other than the alumina particles and the cerium oxide particles may be used singly or in combination of two or more.

The total content of the alumina particles and the cerium oxide particles in the total volume of the inorganic filler is preferably 80% by volume or more, more preferably 90% by volume or more, still more preferably 95% by volume or more, and particularly preferably 98% by volume. %the above.

[hardening accelerator]
The epoxy resin composition of the present disclosure may further contain a hardening accelerator as needed. As the curing accelerator, a general user can be suitably selected and used in the epoxy resin composition for sealing. Examples of the curing accelerator include an organic phosphorus compound, an imidazole compound, a tertiary amine, and a quaternary ammonium salt. Among them, an organic phosphorus compound is preferred. The hardening accelerator may be used alone or in combination of two or more.

Examples of the organic phosphorus compound include organic phosphines such as tributylphosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, methyldiphenylphosphine, and tri-p-tolylphosphine, and the phosphines. A phosphorus compound having intramolecular polarization formed by adding a compound having a π bond such as maleic anhydride, benzoquinone or diazophenylmethane (for example, an adduct of triphenylphosphine and phenylhydrazine, and three pairs of toluene) Addition of phosphine to phenylhydrazine); tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, triphenyl鏻-triphenylborane and the like. When an organophosphorus compound is used as a hardening accelerator, there is a tendency for high reliability in an electronic component device sealed with an epoxy resin composition. Although the reason is not clear, it can be considered as follows. In general, when the epoxy resin composition contains alumina particles, the curability is lowered, so that the amount of use of the curing accelerator tends to increase. However, when the amount of the hardening accelerator is increased, the amount of chlorine ions generated by the reaction of chlorine derived from epichlorohydrin which is a raw material of the epoxy resin and the hardening accelerator may increase, thereby making the electronic component device Reduced reliability. On the other hand, it is considered that the reactivity of the organophosphorus compound is not so high. Therefore, when an organophosphorus compound is used as the curing accelerator, the reaction with chlorine can be suppressed, so that generation of chloride ions can be suppressed, and reliability can be suppressed. reduce. Further, in the epoxy resin composition of the present invention, a phenolic curing agent having a hydroxyl group equivalent of 120 g/eq or less is used. Therefore, even if an organic phosphorus compound is used, the curability is excellent, and good moldability tends to be obtained.

When the epoxy resin composition contains a curing accelerator, the content of the curing accelerator is not particularly limited. For example, it is preferably 1.0% by mass to 10% by mass based on the total amount of the epoxy resin and the curing agent. It is preferably from 1.5% by mass to 7% by mass, and more preferably from 2.0% by mass to 6% by mass.

[Organic solvents]
The epoxy resin composition of the present disclosure may also contain an organic solvent. When the epoxy resin composition contains an organic solvent, the viscosity of the composition tends to decrease, and the kneadability and fluidity tend to be improved. The organic solvent is not particularly limited, and for example, it may contain an organic solvent having a boiling point of from 50 ° C to 100 ° C (hereinafter also referred to as a specific organic solvent).

The specific organic solvent is not particularly limited, and for example, has a boiling point of from 50 ° C to 100 ° C, and is preferably selected from the group which is not reactive with the components in the epoxy resin composition. The specific organic solvent may, for example, be an alcohol solvent, an ether solvent, a ketone solvent or an ester solvent. Among them, an alcohol solvent is preferred, and methanol (boiling point: 64.7 ° C), ethanol (boiling point: 78.37 ° C), propanol (boiling point: 97 ° C), and isopropyl alcohol (boiling point: 82.6 ° C) are more preferred. The specific organic solvent may be used alone or in combination of two or more. Further, the specific organic solvent may be added during the preparation of the epoxy resin composition, or may be produced in the reaction of the kneading process in the preparation of the epoxy resin composition. Furthermore, the boiling point of a specific organic solvent in the present disclosure means the boiling point of a specific organic solvent measured under normal pressure.

The content rate of the specific organic solvent in the epoxy resin composition is not particularly limited. For example, the content of the specific organic solvent is preferably from 0.1% by mass to 10% by mass based on the total mass of the epoxy resin composition, and more preferably from 0.3% by mass to 4.0% by mass from the viewpoint of further improving thermal conductivity. Further, it is preferably from 0.3% by mass to 3.0% by mass, particularly preferably from 0.3% by mass to 2.5% by mass. When the content of the specific organic solvent is 0.3% by mass or more, the effect of improving the fluidity tends to be further improved. When the content of the specific organic solvent is 3.0% by mass or less, the occurrence of voids is further suppressed when the epoxy resin in the epoxy resin composition is cured, and the decrease in insulation reliability tends to be further suppressed.

The content rate of the alcohol solvent in the specific organic solvent is not particularly limited. For example, the content of the alcohol-based solvent is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the specific organic solvent. Further, the epoxy resin composition may not substantially contain a specific organic solvent other than the alcohol solvent.

[additive]
The epoxy resin composition may contain an anion exchanger, a mold release agent, a flame retardant, a coupling agent, a stress relieving agent, a plasticizer, a colorant, and the like as needed.

(anion exchanger)
The epoxy resin composition may also contain an anion exchanger as needed. In particular, when the epoxy resin composition is used as a sealing material, it is preferable to contain an anion exchanger from the viewpoint of improving the moisture resistance and high-temperature placement characteristics of the electronic component device including the sealed component.

The anion exchanger is not particularly limited and can be selected from the general users in the prior art. For example, a hydrotalcite compound and an aqueous oxide of an element selected from the group consisting of magnesium, aluminum, titanium, zirconium and hafnium can be cited.

The anion exchanger is not particularly limited and can be selected from the general users in the prior art. Examples of the anion exchanger include a hydrotalcite compound having a composition represented by the following formula (I) and an aqueous oxide selected from the group consisting of magnesium, aluminum, titanium, zirconium, hafnium and tantalum. The anion exchanger may be used alone or in combination of two or more.

Mg _{1- x} Al _x (OH) ₂ (CO ₃ ) _{x /2} • mH ₂ O (I)

(0<X≦0.5, m is a positive number)

The hydrotalcite compound is a compound having a property of capturing an anion such as a halogen ion by substitution with CO ₃ in the structure, and the halogen ion sucked into the crystal structure is not desorbed until the crystal structure is destroyed at about 350 ° C or higher. . Examples of the hydrotalcite having such properties include Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O produced as a natural product, and Mg _4.3 Al ₂ (OH) _12.6 CO ₃ ·mH ₂ as a synthetic product. O and so on.

Since the epoxy resin composition of the present invention contains a phenol curing agent as a curing agent, the epoxy resin composition exhibits acidity due to the influence of the phenol curing agent (for example, the pH of the extract of the cured product using pure water becomes 3 to 5). ). In this case, for example, aluminum as an amphoteric metal is an environment which is easily corroded by an epoxy resin composition, but the epoxy resin composition contains a hydrotalcite compound which also functions to adsorb acid, and has an aluminum inhibiting property. The tendency to corrode.

Further, an aqueous oxide selected from at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, hafnium and tantalum may also be used to capture anions such as halogen ions by substitution with hydroxide ions. Further, these ion exchangers exhibit excellent ion exchange ability on the acidic side. Therefore, the epoxy resin composition contains these ion exchangers, and similarly to the case of containing a hydrotalcite compound, corrosion of aluminum can be suppressed. Examples of the aqueous oxide include MgO·nH ₂ O, Al ₂ O ₃ ·nH ₂ O, ZrO ₂ ·H ₂ O, Bi ₂ O ₃ ·H ₂ O, and Sb ₂ O ₅ ·nH ₂ O.

When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger is not particularly limited as long as it is a sufficient amount to capture an anion such as a halogen ion. When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger is preferably, for example, 0.1% by mass to 30% by mass, and more preferably 1.0% by mass to 5% by mass.

(release agent)
The epoxy resin composition may contain a release agent as needed, from the viewpoint of exhibiting good mold release property to the mold in the molding step. The type of the release agent is not particularly limited, and a release agent known in the art can be cited. Specific examples of the release agent include higher fatty acids such as palm wax, octadecanoic acid, and stearic acid, ester waxes such as higher fatty acid metal salts and octadecanoic acid esters, oxidized polyethylene, and non-oxidized polyethylene. Polyolefin wax, etc. Among them, palm wax and polyolefin wax are preferred. The release agent may be used alone or in combination of two or more.

A commercially available product can be used as the polyolefin-based wax, and examples thereof include low-molecular-weight polyethylene having a number average molecular weight of about 500 to 10,000 such as H4, PE, and PED series from Hoechst Co., Ltd., and the like.

When the epoxy resin composition contains a polyolefin-based wax, the content of the polyolefin-based wax is preferably 0.01% by mass to 10% by mass, and more preferably 0.10% by mass to 5% by mass based on the epoxy resin. When the content of the polyolefin-based wax is 0.01% by mass or more, sufficient mold release property tends to be obtained, and when it is 10% by mass or less, sufficient adhesiveness tends to be obtained.
Further, when the epoxy resin composition contains a release agent other than the polyolefin-based wax, or when the epoxy resin composition contains a polyolefin-based wax and another release agent, the epoxy resin is used. The content of the other release agent other than the polyolefin-based wax is preferably from 0.1% by mass to 10% by mass, and more preferably from 0.5% by mass to 3% by mass.

(flame retardant)
From the viewpoint of imparting flame retardancy, the epoxy resin composition may contain a flame retardant as needed. The flame retardant is not particularly limited, and examples thereof include known organic compounds and inorganic compounds containing a halogen atom, a ruthenium atom, a nitrogen atom or a phosphorus atom, a metal hydroxide, and an acenaphthylene. The flame retardant may be used alone or in combination of two or more.

In the case where the epoxy resin composition contains a flame retardant, the content of the flame retardant is not particularly limited as long as it is an amount at which a flame retarding effect can be obtained. When the epoxy resin composition contains a flame retardant, the content of the flame retardant is preferably from 1% by mass to 30% by mass, and more preferably from 2% by mass to 15% by mass based on the epoxy resin.

(coupling agent)
From the viewpoint of improving the adhesion between the resin component and the inorganic filler, the epoxy resin composition may contain a coupling agent as needed. The kind of the coupling agent is not particularly limited. Examples of the coupling agent include various decane compounds such as epoxy decane, decyl decane, amino decane, alkyl decane, ureido decane, methacryl decane, acryl decane, and vinyl decane, and titanium compounds. Chelating aluminum compounds, compounds containing aluminum and zirconium, and the like. The coupling agent may be used alone or in combination of two or more.

When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably from 0.05% by mass to 5.0% by mass, and more preferably from 0.10% by mass to 2.5% by mass, based on the inorganic filler. When the content of the coupling agent is 0.05% by mass or more, the adhesion to the frame tends to be improved, and when it is 5.0% by mass or less, the moldability of the package tends to be excellent.

(stress mitigator)
The epoxy resin composition may contain a stress relieving agent such as an anthrone or an anthrone rubber particle as needed, from the viewpoint of reducing the amount of warpage of the package and the crack of the package. As the stress relaxation agent which can be used, a known flexible agent (stress relaxation agent) generally used in the art can be used as appropriate.

Specific examples of the stress relieving agent include thermoplastic elastomers such as anthrone, polystyrene, polyolefin, polyurethane, polyester, polyether, polyamine, and polybutadiene; and natural rubber , NR), acrylonitrile butadiene rubber (NBR), acrylic rubber, urethane rubber, anthrone powder and other rubber particles; methyl methacrylate-styrene-butadiene copolymer Rubber particles having a core-shell structure such as (MBS), methyl methacrylate-anthrone copolymer, methyl methacrylate-butyl acrylate copolymer, and the like. Among them, an anthrone-based stress buffering agent containing an anthrone is preferable. Examples of the anthrone-based stress relaxation agent include those having an epoxy group and those having an amine group, and those obtained by modifying the polyether. The stress relieving agents may be used alone or in combination of two or more.

(Plasticizer)
The epoxy resin composition may also contain a plasticizer from the viewpoint of lowering the high temperature elastic modulus. Examples of the plasticizer include an organic phosphorus compound such as a trialkylphosphine oxide or a phosphate ester, and an anthrone. The content of the plasticizer is preferably 0.001% by mass to 20% by mass, and more preferably 10% by mass to 20% by mass based on the epoxy resin. The plasticizers may be used alone or in combination of two or more.

(Colorant)
The epoxy resin composition may also contain a coloring agent such as carbon black, fibrous carbon, an organic dye, an organic coloring agent, titanium oxide, lead dan, or iron oxide. When the epoxy resin composition contains a colorant, the content of the colorant is preferably from 0.05% by mass to 5.0% by mass, and more preferably from 0.10% by mass to 2.5% by mass, based on the inorganic filler.

[Preparation method of epoxy resin composition]
In the preparation of the epoxy resin composition, any method may be used as long as the various components can be dispersed and mixed. As a general method, the various components are sufficiently mixed by a mixer or the like, and then melt-kneaded by a mixing roll, an extruder, or the like, and cooled and pulverized. More specifically, the epoxy resin composition can be obtained, for example, by mixing and stirring the components, and kneading them by a kneader, a roll, an extruder, or the like which has been previously heated to 70° C. to 140° C. , cooling and pulverizing. The epoxy resin composition can also be tableted in size and quality in accordance with the molding conditions of the package. By ingotning the epoxy resin composition, the operation becomes easy.

[Liquidity of epoxy resin composition]
The epoxy resin composition of the present invention preferably exhibits a flow distance of 160 cm or more when the fluidity is measured by the following method. The epoxy resin composition was molded using a mold for spiral flow measurement according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition was measured. The molding of the epoxy resin composition was carried out under the conditions of a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds using a transfer molding machine.

<Epoxy resin cured>
The cured epoxy resin of the present disclosure is obtained by hardening the epoxy resin composition. The cured epoxy resin of the present invention is obtained by curing the epoxy resin composition, and therefore has excellent moldability and thermal conductivity.

[The thermal conductivity of epoxy resin cured products]
The thermal conductivity of the cured epoxy resin is not particularly limited, but is preferably 2.5 W/(m·K) or more. In the present disclosure, the thermal conductivity of the cured epoxy resin is a value measured as follows. The epoxy resin composition was subjected to transfer molding under the conditions of a mold temperature of 180 ° C, a molding pressure of 7 MPa, and a curing time of 300 seconds to obtain a cured epoxy resin having a mold shape. The specific gravity of the obtained epoxy resin cured product was measured by the Archimedes method, and the specific heat was measured by DSC (for example, Perkin Elmer, DSC Pyris1). Further, the thermal diffusivity of the obtained cured product is measured using a thermal diffusivity measuring device (for example, NETZSCH, LFA 467) by a laser flash method. The thermal conductivity of the cured epoxy resin was calculated using the obtained specific gravity, specific heat, and thermal diffusivity.

<Electronic parts device>
The electronic component device of the present invention has an element, a cured product of the epoxy resin composition of the present invention in which the element is sealed, and has a form of a BGA package. The BGA package is fabricated by mounting an element on a surface of a substrate on which metal bumps are formed on the back surface, and bonding the element to a wiring formed on the substrate by bumping or wire bonding, and then sealing the element. A glass-epoxy printed wiring board etc. are mentioned as a board|substrate. Examples of the element include an active element, a passive element, and the like. Examples of the active device include a semiconductor wafer, a transistor, a diode, a thyristor, and the like. Examples of the passive element include a capacitor, a resistor, a coil, and the like.

In the electronic component device of the present disclosure, the method of sealing the device with the cured epoxy resin is not particularly limited, and a method known in the art can be applied. For example, a low pressure transfer molding method is generally used, and a spray molding method, a compression molding method, or the like can also be used.
[Examples]

Hereinafter, an example of the above embodiment will be specifically described by way of examples, but the invention is not limited to the embodiments.

(Preparation of resin composition)
The components shown below were mixed at the blending ratio (parts by mass) shown in Table 1, and the resin compositions of the examples and the comparative examples were prepared. In Table 1, "-" indicates that the ingredients are not formulated.

·Epoxy resin 1···Biphenyl type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name "YX-4000")
·Epoxy Resin 2···Diphenylmethane Epoxy Resin (Nippon Steel & Sumitomo Chemical Co., Ltd., trade name “YSLV-80XY”)
·Epoxy Resin 3···Multifunctional Epoxy Resin (Mitsubishi Chemical Co., Ltd., trade name “1032H60”)
· Hardener 1··· Polyfunctional phenol resin (AIR WATER, Inc., trade name “HE910”, triphenylmethane phenol resin with a hydroxyl equivalent of 105 g/eq)
- Hardener 2··············································································
·hardening accelerator 1···phosphorus hardening accelerator (organophosphorus compound)

As an inorganic filler, the following is prepared.
Inorganic filler 1: alumina-ceria mixed filler (ceria content: 10% by mass), volume average particle diameter: 10 μm
·Inorganic filler 2: Alumina filler, volume average particle size: 0.8 μm
·Inorganic filler 3: cerium oxide filler, volume average particle diameter: 0.8 μm
·Inorganic filler 4: cerium oxide filler, volume average particle size: 10 μm

Further, as various additives, the following were prepared.
·Coupling agent: Epoxy decane (aniline decane (N-phenyl-3-aminopropyltrimethoxy decane), Shin-Etsu Chemical Co., Ltd., trade name: KBM-573)
·Colorant: Carbon black (Mitsubishi Chemical Co., Ltd., trade name: MA-100)
·Release agent: octadecanoate (Cera Rica NODA Co., Ltd.)

[Table 1]

(evaluation of liquidity)
The evaluation of the fluidity of the epoxy resin composition was carried out by a spiral flow test.
Specifically, the epoxy resin composition was molded using a mold for measuring a spiral flow according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition was measured. The molding of the epoxy resin composition was carried out under the conditions of a mold temperature of 180 ° C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds using a transfer molding machine. In addition, the fluidity is set to A of 160 cm or more and B of less than 160 cm.

(Evaluation of thermal conductivity)
The evaluation of the thermal conductivity when the epoxy resin composition was cured was carried out by the following. Specifically, the prepared epoxy resin composition was subjected to transfer molding under the conditions of a mold temperature of 180 ° C, a molding pressure of 7 MPa, and a curing time of 300 seconds to obtain a cured product having a mold shape. The specific gravity obtained by measuring the obtained hardened material by the Archimedes method was 3.00. The specific heat of the obtained hardened material was measured by DSC (Perkin Elmer, DSC Pyris 1). Further, the thermal diffusivity of the cured product was measured by a laser flash method using a thermal diffusivity measuring device (NETZSCH, LFA467). The thermal conductivity of the cured epoxy resin was calculated using the obtained specific gravity, specific heat, and thermal diffusivity. A thermal conductivity of 2.5 W/(m·K) or more is set to A, and less than 2.5 W/(m·K) is set to B.

[Table 2]

According to Table 2, the ratio of the content of the cerium oxide particles containing the curing agent 1 and the inorganic filler in the range of 65% by volume to 85% by volume and the total amount of the alumina particles and the cerium oxide particles is 10% by mass. In Examples 1 to 3 in the range of ～15% by mass, any evaluation of fluidity and thermal conductivity was good.

The entire disclosure of Japanese Patent Application No. 2017-254880 is incorporated herein by reference.
All the documents, patent applications, and technical specifications described in the present specification are specifically and individually described as being incorporated by reference to the respective documents, patent applications, and technical specifications. Into this specification.

no

no

Claims (6)

An epoxy resin composition for sealing a ball grid array package, comprising an epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g/eq or less, and an inorganic filler containing alumina particles and cerium oxide particles, The content of the inorganic filler is from 65% by volume to 85% by volume. The ratio of the cerium oxide particles to the total amount of the alumina particles and the cerium oxide particles is 10% by mass to 15% by mass. The epoxy resin composition for sealing a ball grid array package according to claim 1, further comprising a curing accelerator, wherein the curing accelerator contains an organic phosphorus compound. The epoxy resin composition for sealing a ball grid array package according to claim 1 or 2, wherein the phenolic hardener comprises a phenol resin having three or more phenolic hydroxyl groups in one molecule. The epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 3, wherein the phenol curing agent comprises a triphenylmethane type phenol resin. An epoxy resin cured product obtained by curing an epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 4. An electronic component device having an element, and an epoxy resin cured product according to claim 5, which is sealed with the element, and has a form of a ball grid array package.